Unique wine flavor protector

ABSTRACT

A stopper for use in a substantially cylindrical bottle opening is disclosed. The stopper is made of a natural cork body with a polymeric portion to prevent flavor scalping and seal the bottle opening. The stopper of the present invention is designed to enhance traditional bark corks in wine bottles. The stopper of the present invention reduces flavor scalping, water and ethanol permeation, and TCA permeation associated with traditional corks, and results in excellent Wine Protection Factor ratings. The method of producing a stopper for use in a substantially cylindrical bottle opening is also disclosed

BACKGROUND OF THE INVENTION

Many liquid products such as oils, honey, alcoholic beverages, and thelike, are sold with stoppered closures, such as corks. Most wine bottleclosures or stoppers have been produced from a natural material known as“cork”. Natural cork has high resiliency properties that make it anexcellent closure for containers with an elasticity which enables rapidrecovery to its original shape after any deformation. Thus, its naturalclosure properties and traditional appearance make cork the preferredbottle closure for wine storage, particularly for medium and highquality wines where adequate closure properties and traditionalappearance are important. A suitable wine stopper must also be able towithstand pressure build-up, pressure fluctuations that naturally occurduring storage, and extraction forces.

Natural corks pose a particular difficulty with wine sold in bottles dueto inherent problems of flavor scalping and taint that sometimes occurin wine. A natural cork is made up of small cells which are configuredto form intercellular spaces. The irregularities of cork cause qualityvariances which result in varying grades of cork based on density andother surface characteristics. Since the texture of cork is not uniform,ducts or openings which are permeable to gases and liquids are ofteninvaded by molds and other microorganisms.

A significant percentage of bottled wine is spoiled by cork taint. Corktaint typically occurs after the wine is bottled, as chemicals ormicroorganisms present in the cork contact and leach into the wine.There are six main chemical compounds associated with cork taint inwines. The most common and readily detectable taint compound is known as2,4,6-trichloroanisole (hereinafter referred to as “trichloroanisole” or“TCA”). TCA is responsible for the offensive malodor and bad flavorassociated with “corked” wine. TCA is analytically detectable atconcentrations as low as 0.5 parts per trillion (ppt) or 0.5 nanogramper liter. Another problem commonly found with natural cork is flavorscalping. Flavor scalping is caused by absorption of wine flavorcompounds by the cork or closure. Many of the closure materialstraditionally used to prevent cork taint also remove flavor compoundsfrom the wine. Additionally, cork impurities and compounds associatedwith synthetic materials applied to the cork are often able to leachinto the wine causing flavor problems for wine bottlers. Similarly, manyclosure materials that would not interact with the flavor compounds ofthe wine when combined with natural cork would not prevent cork taint.

The present invention provides a cork stopper suitable for wineclosures, which eliminates the problems of flavor scalping and taintassociated with cork and synthetic closures. Furthermore, the corkstopper retains the traditional appearance of a wine cork and is able towithstand forces applied during the bottling process, pressure build upthat naturally occurs during storage, and extraction forces.

SUMMARY OF THE INVENTION

The present invention provides a stopper with a body having at least oneend suited to close a container opening; and a polymer portioncomprising a water and ethanol barrier disposed on said at least one endwherein the stopper is adapted to conform to and seal a containeropening. The polymer portion may comprise a multi-layer barrier filmcomprising at least one fluoropolymer based water and ethanol barrierand at least one aroma barrier layer. The multi-layer barrier film mayfurther comprise a fluoropolymer tie layer, bonding the fluoropolymerbased barrier layer to the aroma barrier layer. An adhesive layer may beused to join the aroma barrier layer to the stopper body.

The stopper body may comprise cork and the polymer portion may have aflavor scalp factor of less than 2.0 and daily water permeation factorsof less than 6.0 g/m² per mm thickness. The stopper may further providea flavor scalp factor of less than 2.0 in conjunction with a TCApermeation factor of less than 4.0 percent.

In certain embodiments the stopper comprises a cork body having at leastone end suited to close a container opening; and a multi-layered polymerportion comprising polytetrafluoroethylene (PTFE),polychlorotrifluoroethylene (PCTFE) or other suitable fluoropolymerbased layer disposed on said at least one end wherein the stopper isadapted to conform to and seal said container opening.

In other certain embodiments, the stopper comprises a cork body havingat least one end suited to close a container opening; and amulti-layered polymer portion comprising PTFE and ethylene vinyl alcoholdisposed on said at least one end, wherein the stopper is adapted toconform to and seal said container opening.

DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a stopper comprising a cylindrical body and a polymerportion covering both ends.

FIG. 2 shows a cross section of the polymer portion.

FIGS. 3A-3E show schematic representations of polymeric portions of thepresent invention and stopper surfaces.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a unique flavor protective stopper with abody having at least one end suited to close a container opening; and apolymer portion comprising a water and ethanol barrier, preferablyfluoropolymer based, disposed on said at least one end, wherein thestopper is adapted to conform to and seal a container opening. Thepolymer portion may comprise a multi-layer barrier film with at leasttwo layers. The multi-layer barrier film may comprise at least onefluoropolymer based water and ethanol barrier and at least one aromabarrier. The multi-layer barrier film may further comprise afluoropolymer tie layer, bonding the water and ethanol barrier layer tothe aroma barrier layer. An adhesive layer may be used to join the aromabarrier layer to the stopper body. Suitable water and ethanol barriersinclude: polypropylene (PP), polyethylene (PE) and other relatedcopolymers, polyester (PES), polyethylene terephthalate (PET),polyvinylidene chloride (PVdC), polyvinylidene fluoride (PVdF), Saranex,type barriers (PVdC multi-layered films), polytetrafluoroethylene(PTFE), polychlorotrifluoroethylene (PCTFE), ethylenetetrafluoroethylene (ETFE), ethylene chloro-trifluoroethylene (ECTFE),fluorinated ethylene propylene (FEP), Perfluoro alkoxy vinyl ether(PFA), and other suitable fluoropolymers. The present invention isunique in many different aspects including strength, barrier propertiesand flavor inertness. The high strength allows the multi-layered barrierto maintain its performance after being compressed and forcefullyinserted into the opening of the wine bottle. The high strength providesbarrier integrity and also allows for a more robust manufacturingprocess and provides one of the strongest, thinnest moisture barriersavailable.

FIG. 1 shows a stopper 1 comprising a body 3 having a top end 5 and abottom end 7 with at least one side portion 9 located between the topend 5 and the bottom end 7. At least one end of the body 3 is coveredwith a polymer portion 10 comprising a fluoropolymer. In a preferredembodiment, the polymer portion 10 is adhered to the at least one endand a side portion 9 of the body 3. The polymer portion 10 may beadhered in part or whole to the surface of the at least one end, oralternatively, only the perimeter of the polymer portion 10 may beadhered to the body 3. In some desired applications, the polymericportion covers between 2 and 10 mm up the side of the cork body 3. In apreferred embodiment, the polymer portion 10 is not adhered at interfacebetween the body 3 and the end of the cork. It is preferred that atleast 25 percent of the polymer portion 10 is adhered to the body 3surface. In one aspect, the present invention is able to provide atransparent polymer portion 10 which is highly undetectable when adheredto a natural cork, thus preserving the aesthetic value of natural corks.

The polymer portion 10 comprises at least two parts, namely (a) a waterand ethanol barrier 40 such as a PTFE film and (b) an aroma barrier 18such as an ethylene vinyl alcohol copolymer film, subsequently referredto as EVOH, nylons, polyvinylidene chloride (PVDC), polypropylene andfluoroethylene based materials, such as tetrafluoroethylene (TFE);ethylene tetrafluoroethylene (ETFE), ethylene chloro-trifluoroethylene(ECTFE), polychlorotrifluoroethylene (PCTFE); and other suitablematerials. The polymer portion 10 may exist as a multi-layered filmwhich is bonded together with a tie layer 20. The tie layer 20 may beany suitable material which joins the polymer portion 10 to the aromabarrier 18. Examples include fluoropolymer layers, adhesives,thermoplastics, and the like. The polymer portion 10 is disposed over atleast one end of the stopper 1 and adapted to conform to and seal anopening in a bottle neck. The body 3 of the stopper 1 is comprised ofnatural cork in a preferred embodiment, but other types of materials maybe used, including agglomerated cork, polyolefins, or other syntheticmaterials. The most common stoppers are cylindrical in form, but othershapes are contemplated and may be employed by the present invention

FIG. 2 shows a cross section of the polymer portion 10. The polymerportion 10 is depicted as a multi-layer barrier film which protects thecontents of a container from flavor and/or taste influences. The presentinvention is particularly useful for natural wine corks, especially forpreventing 2,4,6-trichloroanisole (TCA) taint from natural cork, andflavor scalping common with natural and synthetic closures. Previousattempts to prevent TCA contamination by shutting off one mechanism ofpermeation, either diffusion or solubility, have been largelyunsuccessful. It has been found that the mechanism of TCA contaminationof wine is the combination of permeation and solubility. Fluoropolymerbased water and ethanol barriers and aroma barriers individually do notprevent TCA contamination, but the combination of the two barriersappears to be much more effective. A multi-layer polymer portion 10adhered to a closure can prevent permeation and extraction of taintcaused by TCA and other wine contaminants. For instance, an aromabarrier 18 prevents the diffusion of TCA and tainting compounds from thecork across the water and ethanol barrier into the wine. As an example,a PTFE based water and ethanol barrier is able to prevent thesolubilization of EVOH by water and ethanol, thus preventing theextraction of TCA from the cork into the contents of the wine via waterand ethanol.

Surprisingly, the present invention keeps the product flavors pristinein that flavors are neither added nor removed from the product by thestopper 1. Polymers that do not absorb flavors are typically highlycrystalline. Many highly protective aroma barriers are crystalline buttypically hydrolyze in wine over time and thus reduce their barrierproperties, lose their inherent strength, or absorb flavors. The presentinvention provides a polymer portion which is strong, flexible, andcrystalline but does not absorb flavors. There are also no flavors addedto the contents of the stoppered container, nor are there extractablespresent. As shown in the examples, compared to several other standardfood packaging films, fluoropolymer based water and ethanol barrierssuch as polytetrafluoroethylene did not exhibit a recognizable flavordifference when tested in wine.

As shown in FIG. 2, the multi-layer barrier film 15 is comprised of atleast two layers, an outer water and ethanol barrier 40, preferablyfluoropolymer based, and an aroma barrier 18 layer. As shown in FIGS.3A-3E different configurations of the polymer portion 10 may beassembled which are in accordance with the present invention. Forinstance, a three-layer multi-barrier film may be formed by adding anadhesive 22 layer to the fluoropolymer layer and aroma barrier 18layers. In a preferred embodiment, the multi-layer barrier film iscomprised of at least four layers, an outermost fluoropolymer layer, atie layer, an aroma barrier 18 layer, and an adhesive 22 layer to bondthe film to the stopper or cork body 3. The entire polymer portion 10 iscrystalline to provide barrier and flavor inertness properties. Themulti-layer barrier film may be present covering the surface of thecork, or alternatively may infiltrate the interstices of the cork toprovide a filled surface.

The fluoropolymer based water and ethanol barrier layer is the outermostlayer on the film and is hydrophobic, food safe, non-flavor absorbing,and provides water and ethanol barrier properties. The low water andethanol permeability of the fluoropolymer layer provides low relativehumidity at the aroma barrier 18 layer, maintaining the permeationperformance of aroma barriers, such as EVOH. The water and ethanolbarrier properties of the fluoropolymer layer also prevent wine(approximately 13 percent ETOH, >80 percent H₂O) from permeating intothe cork, solubilizing TCA and extracting the TCA back across and intothe wine. Suitable examples of a fluoropolymer based barrier layerinclude PTFE, PCTFE, ETFE, ECTFE, FEP, PFA, PVdF. The fluoropolymerbarrier layer helps provide the polymer portion 10 with strength andalso provides protection from the industrial bottling process to thelayers beneath and prevents the take-up of flavors from wine. In certainembodiments, the fluoropolymer layer may be coated on to the ends of astopper body. One example of this would be PTFE coated on the ends of acork or other stopper.

A tie layer 20 is in contact with the fluoropolymer layer. Suitable tielayers include, but are not limited to, fluorinated ethylene propylenecopolymers, perfluoroalkoxy copolymers, ethylene tetrafluoroethylene,polyethylene, polyurethanes, silicones, EVA, polyvinylidenechloride,polyvinylidenefluoride, polychlorotrifluoroethylene, ECTFE, andcombinations thereof. A tie layer 20 provides a heat bondable surface toadhere the water and ethanol barrier to the aroma barrier 18. Thefluoropolymer based tie layer 20 must also be food safe, have noextractable compounds, and be non-absorbing of flavors and aromas. It isa further option to remove the fluoropolymer based tie layer 20 and bondthe aroma barrier 18 directly to the outer water and ethanol barrierlayer when using a fluoropolymer based water and ethanol barriersuitable for direct bonding.

The aroma barrier 18 layer is located between the water and ethanolbarrier layer and the stopper 1. The aroma barrier 18 prevents flavorchanges from occurring as well as maintaining the scents desirable inquality wines. PCTFE and EVOH both provide very good aroma and flavorbarrier properties. PCTFE is used in pharmaceutical packagingapplications. EVOH is used in food packaging applications such asplastic toothpaste tubes and ketchup bottles. It performs best whenprotected and kept in a low relative humidity environment. It has beenfound that matching the aroma barrier 18 with a strong, flexiblefluoropolymer based moisture and ethanol barrier maintains a lowrelative humidity at the EVOH layer and provides barrier integrity. TheEVOH provides permeation resistance against TCA, preventing TCA fromdiffusing from the cork matrix into the wine.

An adhesive 22 layer may be used to adhere the aroma barrier 18 layer tothe body 3, such as natural or synthetic cork. In a preferredembodiment, the aroma barrier 18 layer is also in contact with the tielayer 20 which ties it to the water and ethanol barrier layer. Theadhesive 22 layer is preferably an EVOH film with ethylene contentsufficient to achieve an adequate bond (measured by peel strength)between the EVOH and the natural cork surface. Preferably, the adhesive22 layer has a lower melting temperature than the melting temperaturesof the aroma barrier layer. In one preferred embodiment, the adhesive 22layer is an extruded commercial EVOH film that is heat laminated to asecond EVOH film which provides aroma barrier properties. Other suitableadhesive 22 layers such as polyethylene, polyurethane, or ethyl vinylacetate need to be food safe, hydrolysis resistant, and provide adequatebond strength. A layer is considered to be a continuous or discontinuousplanar portion comprising essentially one material or combination ofmaterials. The material may be homogeneous or non-homogenous in nature.Additionally, the adhesive 22 may attach the barrier to the body 3 in acontinuous or discontinuous manner.

The present invention provides overall barrier properties such as waterand ethanol barrier desirable for wine storage. PTFE based water andethanol barriers are very good barriers for polar compounds making it agood moisture barrier and also a good ethanol barrier. Many commercialbarrier films are good moisture barriers, but in the presence ofthirteen percent ethanol (typical wine concentration) some good moisturebarriers lose effectiveness. Moisture barriers such as nylon,polyvinylidene chloride, and polyethylene have a loss in moisturebarrier performance of roughly 10-100 times their original properties inthe presence of ethanol. The water permeation properties offluoropolymer films, such as PTFE, are not significantly changed by theaddition of 13 percent ethanol into solution. This is important becauseTCA is readily soluble in ethanol and the fluoropolymer based water andethanol barriers prevent the permeation of ethanol into the cork,preventing TCA from being extracted from the cork into the wine.Further, the combination of a hydrophobic fluoropolymer based water andethanol barrier with the EVOH based aroma barrier maintains a lowhumidity at the EVOH surface, allowing the EVOH to provide aroma barrierproperties.

FIGS. 3A-3C show various cross sectional views of the polymer portion 10of the present invention. In FIG. 3A, the water and ethanol barrierlayer 40 is bonded to an aroma barrier 18 layer without the use of a tielayer 20. The aroma barrier 18 is then joined to the stopper 1 surfacevia an adhesive 22. FIG. 3B shows a tie layer 20 present connecting thewater and ethanol barrier layer and the aroma barrier 18 layer. Thearoma barrier 18 is then joined to the stopper 1 surface via an adhesive22.

FIG. 3C shows an asymmetric fluoropolymer barrier film wherein the innerside of the fluoropolymer barrier film comprises a more porous structureinto which the aroma barrier 18 layer is at least partially penetrated.

FIG. 3D shows a polymer portion joined to the surface of the stopperbody 3, without a tie layer. In FIG. 3E, the polymer portion 10 of awater and ethanol barrier layer 40 and aroma barrier 18 are joined via atie layer 20 and then contacted to the stopper 1 without the need foradhesive.

A wine protection factor associated with flavor and taint is describedat Example 4. A good quality wine is considered to score greater thanforty.

In one aspect, the present invention provides a stopper 1 with a corkbody 3 having a flavor scalp factor of less than 2.0 and a daily waterpermeation factor of less than 6.0 g/m² per mm thickness. In anotheraspect, the present invention provides a stopper 1 comprising a corkbody 3 having a flavor scalp factor of less than 2.0 and a TCApermeation factor of less than 4.0 percent. In yet another aspect of thepresent invention, a stopper 1 is provided comprising a cork body 3having a daily water permeation factor of less than 6.0 g/m² per mmthickness and a TCA permeation factor of less than 4.0 percent.

A wine protection factor may be computed by considering flavor scalpingeffects, TCA permeation, and water permeation. As shown in FIG. 3, thewine protection factor may be computed as:

$\frac{100}{\begin{matrix}\left\lbrack {{{Scalp}\mspace{14mu} {Factor}} + {{TCA}\mspace{14mu} {Permeation}\mspace{14mu} {Factor}} +} \right. \\\left. {{Water}\mspace{14mu} {Permeation}\mspace{14mu} {Factor}} \right\rbrack\end{matrix}}$

In this manner the total protection output of a barrier may be comparedto other barriers. It has been found that an ideal wine protectionfactor for wine is greater than forty.

Traditionally, the six main chemical compounds associated with flavorscalping in wines are Ethyl Hexanoate (eH), Ethyl Octanoate (eO), EthylDecanoate (eD), Rose Oxide (RO), Damascenone (D), and Beta Ionone (BI).TDN and naphthalene are additionally widely regarded as measurableflavor factors. However, it is unclear if removal of these two compoundsenhances or diminishes the quality of wine. Therefore, for the purposeof the present invention, they have not been included as measured scalpfactors. It has been found to be desirable that the multi-layer barrierfilm portion of the stopper 1 has a scalping percentage for eH of lessthan 0.9. The multi-layer barrier film portion of the stopper 1 has ascalping percentage for eO of less than 0.9. The multi-layer barrierfilm portion of the stopper 1 has a scalping percentage for eD of lessthan 3.0. The multi-layer barrier film portion of the stopper 1 has ascalping percentage for D of less than 0.9. The multi-layer barrier filmportion of the stopper 1 has a scalping percentage for BI of less than2.0.

The most common taint compound found in natural corks is known as2,4,6-trichloroanisole (TCA). It is preferred that the amount of TCAthat is allowed to leach into the wine is less than 5 nanograms perliter of wine.

In one embodiment of the present invention, the stopper comprises a corkbody having at least one end suited to close a container opening; and amulti-layered polymer portion 10 comprising PTFE or PCTFE or SARANEX™disposed on said at least one end, wherein the stopper is adapted toconform to and seal said container opening. A tie layer may be presentif desired.

Similarly, in another embodiment of the present invention, the stoppercomprises a cork body having at least one end suited to close acontainer opening; and a multi-layered polymer portion comprising PTFEand ethylene vinyl alcohol disposed on said at least one end wherein thestopper is adapted to conform to and seal said container opening.

In these embodiments, it is advantageous that the wine protection factoris greater than 20, and even more advantageous that the wine protectionfactor is greater than forty. The multi-layer barrier film portion ofthe stopper 1, not including the adhesive 22, is able to be constructedto a thickness of less than 0.035 mm.

While particular embodiments of the present invention have beenillustrated and described herein, the present invention should not belimited to such illustrations and descriptions. It should be apparentthat changes and modifications may be incorporated and embodied as partof the present invention within the scope of the following claims.

EXAMPLES Example 1 Cork Taint Testing

Evaluation of the ability to prevent TCA contamination was conducted atETS labs in St. Helena, Calif. ETS is a privately owned wine analyticallaboratory, located in Napa valley (ETS Laboratories, 899 Adams St.,Suite A, St. Helena, Calif. 94574) and has a unique expertise in TCAanalysis. ETS has developed a TCA QC method called releasable TCA (rTCA)for the Cork Quality Council and has established the test as a globalTCA QC tool using gas chromatograph-mass spectroscopy (GCMS).Traditional TCA test methods were destructive, but the releasable TCAtest is not. The rTCA test is based on the effect that a cork releasesthe same amount of TCA when soaked in wine to reach a repeatableequilibrium concentration. This releasable TCA amount reachesequilibrium in the first 24 hours and is repeatable 100 times or more.In the trial, 400 natural corks were each spiked with 100 ng of TCA. Thecorks were grouped into 20 bulks (groups) of 20 corks and each bulk wastested for releasable TCA via GCMS. ETS found rTCA numbers in the rangeof 5 to 30 nanograms TCA/L, which is typical for naturally contaminatedcorks. After the bulk test was performed, each individual cork in a bulkwas wrapped with a barrier material. Each bulk of 20 corks was wrappedwith the same barrier

TABLE 1 TCA PERMEATION FACTORS FOR VARIOUS BARRIER FILMS RELEASABLERELEASABLE TCA TCA TCA PERMEATION NO BARRIER W/ BARRIER FACTOR MATERIAL(ng TCA/L) (ng TCA/L) (%) PTFE + EVOH 35.30 0.00 0.00 PCTFE + EVOH 40.051.20 0.03 FEP + EVOH 44.80 4.00 0.09 Saranex23 38.35 0.00 0.00 Nylon +EVOH 45.35 9.90 0.22 EVOH 35.20 27.30 0.78material. The 20 individually wrapped corks of the same material werethen recombined into a bulk and soaked to determine the Releasable TCA(rTCA) with the barrier present. The results of the cork taint analysis(TCA) of selected material used in the test are shown below in table 1.

Multiple barrier materials were used, including PTFE, FEP, Nylon6, EVOH,Saranex 23, PCTFE, and combinations thereof. Materials were obtainedfrom Goodfellow Corp. (Goodfellow Corp., 237 Lancaster Ave., Suite 252,Devon, Pa. 19333) and EVALCA (EVALCA NA., 2625 Bay Area Blvd., Suite300, Houston, Tex. 77058). The materials were soaked in a control winefor 12 weeks at room temperature and the releasable TCA was thenmeasured to determine the ratio of TCA detected initially without abarrier to the TCA detected with a barrier. The TCA permeation factor isdefined as the ratio of the amount of TCA measured in the wine aftersoaking with the barrier present to the amount of TCA measured in thewine without the barrier.

Example 2 Moisture Vapor Permeation Testing

To judge the performance of the water/ethanol barrier, we testedmultiple combinations of barrier films at MOCON Labs (MOCON INC., 7500Boone Ave. North, Minneapolis, Minn. 55428) that specializes inpermeation testing. Experiments were conducted to determine the moisturebarrier performance of various food packaging barrier materials in thepresence of ethanol. Scientific literature provides water vaporpermeation values for each of the barrier materials. To prove ourconcept that barrier performance is not compromised when placed incontact with wine, each material was challenged with a permanent of 13percent Ethanol in H₂O. The permeation tests were performed at 25° C.and had 100 percent nitrogen gas, dry at ambient pressure as the carriergas.

The results from MOCON are reported as water vapor transmission rate andcan readily be normalized to thickness to compare different thicknessmaterials. In general, the results show a clear agreement withtheoretical values for water vapor transmission rate. The followingresults below in table 2 illustrate the data from the MOCON testing.

TABLE 2 Water Vapor Transmission Rates normalized for sample thicknessOverall Average WVTR* Thickness WVTR Thickness Material (mm) (g/m²-day)(g-mm/m²-day) PTFE + PolyChloroTriFluoroEthylene (PCTFE) 0.032 0.07650.0024 PTFE + EVOH 0.035 0.1625 0.0057 Untensilized PTFE + EVOH 0.0880.0780 0.0069 PTFE + PolyVinylidene Chloride (PVdC) 0.032 0.2415 0.0077Polypropylene (PP) + EVOH 0.022 0.6575 0.0145 PerFluoroAlkoxy VinylEther(PFA) + EVOH 0.062 0.3275 0.0204 Polyethylene (PE) + EVOH 0.037 0.60650.0227 Floronated Ethylene Propylene (FEP) + EVOH 0.062 0.3720 0.0232LDPE/PVdC/EVA (Saranex 23) 0.051 0.4760 0.0242 Polyamide (Nylon6) + PVDC0.037 0.8955 0.0331 EthyleneTriFluoroEthylene (ETFE) + EVOH 0.062 1.1910.0743 Polyethylene Terephthalate (PET) + EVOH 0.025 3.0815 0.0770Polyamide (Nylon 66) + EVOH 0.062 3.6395 0.2271 Ethylene Vinyl Alcohol(EVOH-XL) 0.012 27.08 0.3250

As observed from the above results, the materials that perform the bestare the PCTFE and PTFE based materials. The key point in this data isthat some of the aroma barrier materials that performed well whencombined with PTFE, such as PCTFE, PVdC, and EVOH, are verydimensionally unstable and not likely strong enough to survive anindustrial bottling process on their own. By combining thesedimensionally unstable materials with the PTFE based water and ethanolbarrier, the integrity and performance of the aroma barriers is greatlyimproved.

Because of the importance of having a barrier to the polar solventsfound in wine that would extract TCA from cork, such as water andethanol, the water vapor transmission rate, normalized to thickness isdefined as our Water Permeation Factor. We have created the WaterPermeation Factor to help build the Wine Protection Factor as thematerial placed on the stopper must be able to withstand water/ethanolwithout degradation and prevent permeation of water/ethanol to the cork.The H₂O Permeation Factors for selected performers from the above listof MOCON samples is shown below in table 3.

TABLE 3 WATER PERMEATION FACTORS FOR VARIOUS BARRIER FILMS H₂O SAMPLEH₂O VAPOR THICK- PERMEATION FLUX NESS FACTOR MATERIAL (g/m²-day) (mm)(mg-mm/m²-day) PTFE + EVOH 0.1625 0.035 0.57 Untensilized PTFE + EVOH0.0780 0.088 0.69 PCTFE + EVOH 0.0885 0.030 0.27 FEP + EVOH 0.3720 0.0622.32 Saranex23 0.4760 0.051 2.42 Nylon + EVOH 3.6395 0.062 22.71 EVOH67.715 0.020 135.43

Example 3 Flavor Compound Scalping Testing

Provisor is an independent testing lab located in Australia (ProvisorPty. Ltd., ABN 41 101 149 482, Hartley Grove, Urrbrae SA 5064) thatspecializes in grape and wine research, and provides analytical testingfor chemical compounds in wine, such as taint and scalp. We providedsamples to Provisor to determine the amount of flavor and aromacompounds removed (scalped) from the wine. Scalp analysis is assessedthrough gas chromatography-mass spectrometry measurements of flavorcompounds remaining relative to an untreated control. The ability of thematerials to not scalp flavors from wine was evaluated using 8 standardflavor compounds. The compounds were ethyl hexanoate, ethyl octanoate,ethyl decanoate, rose oxide, naphthalene, TDN(1,1,6-trimethyl-1,2-dihydronapthalene), damascenone, beta-ionone. Toevaluate each material sample, a wine solution was dosed with a measuredamount of the flavor compound and then the material was soaked in thesolution at a contact ratio of 1:50. A contact ratio of 1:1 submergesthe same closure surface area as that found in a standard bottle ofwine, a contact ratio of 1:50 provides 50 times the closure area ascompared to a standard bottle.

The percent of compound scalped is calculated by applying the followingformula:

100*([Concentration in wine in contact with material]−[Concentration inwine with no added materials])/[Concentration in wine with no addedmaterials],

where both wine solutions have been dosed with the chemicals ofinterest.

To facilitate differentiation between the materials tested, the rawvalues have been included in table 4. Table 4 below shows, for eachmaterial tested, the percent compound scalped for each individualcompound. The scalp factor is defined as the cumulative amount ofscalped compound. The overall trend for the known materials is asexpected with the cork samples showing scalping of all compounds andsignificantly less scalping for SARANEX™ (screw-cap liner). For theother materials, even though many of the values are <10 percent scalped,a cumulative picture facilitates differentiation between materials.

TABLE 4 SCALP FACTORS FOR VARIOUS BARRIER FILMS CHEMICAL SPECIESEXAMINED FOR SCALPING (% scalped) SCALP ETHYL ETHYL ETHYL ROSE OXIDEBETA FACTOR MATERIAL HEXANOATE OCTANOATE DECANOATE ISOMER 1&2DAMASCENONE IONONE (%) PTFE + EVOH 0.0 0.0 1.0 7.0 0.0 1.0 9.0 PCTFE +EVOH 2.0 8.0 16.0 0.0 1.0 2.0 29.0 FEP + EVOH 11.0 4.0 4.0 7.0 0.0 1.027.0 Saranex23 1.0 0.0 18.0 6.0 3.0 9.0 37.0 Nylon6 + EVOH 0.0 0.0 0.01.0 1.0 1.0 3.0 EVOH 0.0 0.0 0.0 0.0 0.0 2.0 2.0 Natural Cork 8.0 15.036.0 5.0 13.0 19.0 96.0 Agglomerate Cork 10.0 21.0 49.0 5.0 16.0 27.0128.0

Example 4 Wine Protection Factor

When evaluating the performance of a closure suitable for applicationswhere wine or other beverages with alcohol are present, a measure thattakes into account the multiple performance facets is desirable. Inaddition to creating a quality seal with the container, the closure mustminimize the amount of flavor compounds added or removed from the wine.The Wine Protection Factor is provided as a means to describe andcompare various closures in the three performance aspects needed for awine closure.

The Wine Protection Factor is computed by the following equation:

$\frac{100}{\begin{matrix}\left\lbrack {{{Scalp}\mspace{14mu} {Factor}} + {{TCA}\mspace{14mu} {Permeation}\mspace{14mu} {Factor}} +} \right. \\\left. {{Water}\mspace{14mu} {Permeation}\mspace{14mu} {Factor}} \right\rbrack\end{matrix}}$

The Wine Protection Factor takes into account the critical performancefeatures of a wine closure and quantifies the three aspects central tothe contamination mechanism of wine: flavor scalping, TCA permeation,and TCA extraction. In this manner the total protection output of abarrier may be calculated as shown below for selected materials:

TABLE 4 WINE PROTECTION FACTORS FOR VARIOUS BARRIER FILMS WINEPROTECTION MATERIAL FACTOR PTFE + EVOH 45.7 PCTFE + EVOH 19.5 FEP + EVOH14.5 Saranex23 11.6 Nylon + EVOH 4.3 EVOH 0.7The Wine Protection Factor provides a comparison by which to determinethe best materials to create closures for wine.

1. A stopper comprising: a) a body having at least one end suited toclose a container opening; and b) a polymer portion comprising at leastone fluoropolymer disposed on said at least one end, wherein the stopperis adapted to conform to and seal said container opening.
 2. The stopperof claim 1, wherein the polymer portion further comprises at least onearoma barrier layer.
 3. The stopper of claim 1, wherein thefluoropolymer is a water and ethanol barrier
 4. The stopper of claim 3wherein the polymer portion is a multi-layer barrier film furthercomprising a fluoropolymer tie layer bonding the water and ethanolbarrier layer to an aroma barrier layer.
 5. The stopper of claim 2further comprising an adhesive layer joining the aroma barrier layer tothe stopper body.
 6. The stopper of claim 1, wherein the body iscomprised of cork.
 7. The stopper of claim 3, wherein the water andethylene barrier layer comprises a polytetrafluoroethylene.
 8. Thestopper of claim 1, wherein the aroma barrier is an ethylene vinylalcohol copolymer film.
 9. The stopper of claim 1, wherein the aromabarrier is a polyvinylidine chloride.
 10. The stopper of claim 1,wherein the aroma barrier is a polypropylene.
 11. The stopper of claim7, wherein the aroma barrier is bonded to the PTFE.
 12. The stopper ofclaim 1, wherein the polymer portion is adhered to the at least one endand a portion of the body.
 13. The stopper of claim 12, wherein thepolymer portion is adhered to the entire face of at least one end. 14.The stopper of claim 13 wherein the perimeter of the polymer portion isadhered to the body.
 15. The stopper of claim 14 wherein the polymerportion is only adhered to a side of the body.
 16. A stopper comprisinga cork body having a flavor scalp factor of less than 2.0 and a dailywater permeation factor of less than 6.0 g/m² per mm thickness.
 17. Astopper comprising a cork body having a flavor scalp factor of less than2.0 and a TCA permeation factor of less than 4.0 percent.
 18. A stoppercomprising a cork body having a daily water permeation factor of lessthan 6.0 g/m² per mm thickness and a TCA permeation factor of less than4.0 percent.
 19. A stopper comprising a cork body having a WineProtection Factor of greater than
 5. 20. A stopper comprising a corkbody having a Wine Protection Factor of greater than
 20. 21. A stoppercomprising a cork body having a Wine Protection Factor of greater thanforty.
 22. The stopper of claim 2, wherein the aroma barrier layercomprises ethylene vinyl alcohol.
 23. The stopper of claim 1, whereinthe Wine Protection Factor is greater than
 5. 24. The stopper of claim1, wherein the Wine Protection Factor is greater than
 15. 25. Thestopper of claim 1, wherein the Wine Protection Factor is greater than20.
 26. The stopper of claim 1, wherein the Wine Protection Factor isgreater than
 40. 27. The stopper of claim 1, wherein the polymericportion is transparent.
 28. The stopper of claim 1, wherein thepolymeric portion is less than 0.035 mm in thickness.
 29. The stopper ofclaim 1, wherein the polymeric portion has a scalping percentage for eHof less than 0.9.
 30. The stopper of claim 1, wherein the polymericportion has a scalping percentage for eO of less than 0.9.
 31. Thestopper of claim 1, wherein the polymeric portion has a scalpingpercentage for eD of less than 3.0.
 32. The stopper of claim 1, whereinthe polymeric portion has a scalping percentage for D of less than 0.9.33. The stopper of claim 1, wherein the polymeric portion has a scalpingpercentage for BI of less than 2.0.
 34. The stopper of claim 1, whereinthe polymeric portion covers a distance of greater than 2 mm on thecylindrical body.
 35. The stopper of claim 1, wherein the polymerportion has a thickness of less than 60 microns across the entirepolymer portion.
 36. The stopper of claim 1, wherein the polymer portionhas a Wine Protection Factor greater than 20 and a thickness of lessthan 60 microns across the entire polymer portion.
 37. The stopper ofclaim 1, wherein the polymer portion extends past the sealing end overthe cylindrical body side for a distance of greater than 1 mm.
 38. Thestopper of claim 2, wherein the aroma barrier layer comprisespolychlorotrifluoroethylene.
 39. A stopper comprising: a) a cork bodyhaving at least one end suited to close a container opening; and b) amulti-layered polymer portion comprising at least onepolytetrafluoroethylene layer and at least one ethylene vinyl alcoholbased layer covering said at least one end, wherein the stopper isadapted to conform to and seal said container opening.
 40. A stoppercomprising: a) a cork body having at least one end suited to close acontainer opening; and b) a polymer portion comprisingpolychlorotrifluoroethylene disposed on said at least one end, whereinthe stopper is adapted to conform to and seal said container opening.41. A stopper comprising: a) a cork body having at least one end suitedto close a container opening; and b) a multi-layered polymer portioncomprising PTFE and ethylene vinyl alcohol disposed on said at least oneend, wherein the stopper is adapted to conform to and seal saidcontainer opening.